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NASA NTRS2001

The Effect of Cytidine on the Structure and Function of an RNA Ligase Ribozyme

A cytidine-free ribozyme with RNA ligase activity was obtained by in vitro evolution, starting from a pool of random- sequence RNAs that contained only guanosine, adenosine, and uridine. This ribozyme contains 74 nt and catalyzes formation of a 3',5' -phosphodiester linkage with a catalytic rate of 0.016/min. The RNA adopts a simple secondary structure based on a three-way junction motif, with ligation occurring at the end of a stem region located several nucleotides away from the junction. Cytidine was introduced to the cytidine-free ribozyme in a combinatorial fashion and additional rounds of in vitro evolution were carried out to allow the molecule to adapt to this added component. The resulting cytidine-containing ribozyme formed a 3',5' linkage with a catalytic rate of 0.32/min. The improved rate of the cytidine-containing ribozyme was the result of 12 mutations, including seven added cytidines, that remodeled the internal bulge loops located adjacent to the three-way junction and stabilized the peripheral stem regions.

Rogers, Jeff↗

NASA NTRS1999

Lean Premixed Combustion Stabilized by Low Swirl a Promising Concept for Practical Applications

Since its inception, the low-swirl burner (LSB) has shown to be a useful laboratory apparatus for fundamental studies of premixed turbulent flames. The LSB operates under wide ranges of equivalence ratios, flow rates, and turbulence intensities. Its flame is lifted and detached from the burner and allows easy access for laser diagnostics. The flame brush is axisymmetric and propagates normal to the incident reactants. Therefore, the LSB is well suited for investigating detailed flame structures and empirical coefficients such as flame speed, turbulence transport, and flame generated turbulence. Due to its capability to stabilize ultra-lean premixed turbulent flames (phi approx. = 0.55), the LSB has generated interest from the gas appliance industry for use as an economical low-NO(x) burner. Lean premixed combustion emits low levels of NO(x), due primarily to the low flame temperature. Therefore, it is a very effective NO(x) prevention method without involving selective catalytic reduction (SCR), fuel-air staging, or flue gas recirculation (FGR). En the gas turbine industry, substantial research efforts have already been undertaken and engines with lean premixed combustors are already in use. For commercial and residential applications, premixed pulsed combustors and premixed ceramic matrix burners are commercially available. These lean premixed combustion technologies, however, tend to be elaborate but have relatively limited operational flexibility, and higher capital, operating and maintenance costs. Consequently, these industries are continuing the development of lean premixed combustion technologies as well as exploring new concepts. This paper summarizes the research effects we have undertaken in the past few years to demonstrate the feasibility of applying the low-swirl flame stabilization method for a wide range of heating and power generation systems. The principle of flame stabilization by low-swirl is counter to the conventional high-swirl methods that rely on a recirculation zone to anchor the flame. In LSBS, flow recirculation is not promoted to allow the premixed turbulent flames to propagate freely. A LSB with an air-jet swirler is essentially an open tube with the swirler at its mid section. The small air-jets generate swirling motion only in the annular region and leaving the central core of the flow undisturbed, When this flow exits the burner tube, the angular momentum generates radial mean pressure gradient to diverge the non-swirling reactants stream. Consequently, the mean flow velocity decreases linearly. Propagating against this decelerating flow, the flame self-sustains at the position where the local flow velocity equals the flame speed, S(sub f). The LSB operates with a swirl number, S, between 0.02 to 0.1. This is much lower than the minimum S of 0.6 required for the high-swirl burners. We found that the swirl number needed for flame stabilization varies only slightly with fuel type, flow velocity, turbulent conditions and burner dimensions (i.e. throat diameter and swirl injection angle).

Cheng, R. K.↗

NASA NTRS2000

Surface Characterization of LMMS Molybdenum Disilicide Coated HTP-8 Using Arc- Jet Hypersonic Flow

Surface properties for an advanced Lockheed Martin Missile and Space (LMMS) molybdenum disilicide coated insulation (HTP-8) were determined using arc-jet flow to simulate Earth entry at hypersonic speeds. The catalytic efficiency (atom recombination coefficients) for this advanced thermal protection system was determined from arc-jet data taken in both oxygen and nitrogen streams at temperatures ranging from 1255 K to roughly 1600 K. In addition, optical and chemical stability data were obtained from these test samples.

Stewart, David A.↗

NASA NTRS2007

Oxygen Generation from Carbon Dioxide for Advanced Life Support

The partial electrochemical reduction of carbon dioxide (CO2) using ceramic oxygen generators (COGs) is well known and widely studied. However, complete reduction of metabolically produced CO2 (into carbon and oxygen) has the potential of reducing oxygen storage weight for life support if the oxygen can be recovered. Recently, the University of Florida devel- oped novel ceramic oxygen generators employing a bilayer elec- trolyte of gadolinia-doped ceria and erbia-stabilized bismuth ox- ide (ESB) for NASA's future exploration of Mars. The results showed that oxygen could be reliably produced from CO2 at temperatures as low as 400 C. The strategy discussed here for advanced life support systems employs a catalytic layer com- bined with a COG cell so that CO2 is reduced all the way to solid carbon and oxygen without carbon buildup on the COG cell and subsequent deactivation.

Bishop, Sean↗

NASA NTRS1996

Surface Catalytic Efficiency of Advanced Carbon Carbon Candidate Thermal Protection Materials for SSTO Vehicles

The catalytic efficiency (atom recombination coefficients) for advanced ceramic thermal protection systems was calculated using arc-jet data. Coefficients for both oxygen and nitrogen atom recombination on the surfaces of these systems were obtained to temperatures of 1650 K. Optical and chemical stability of the candidate systems to the high energy hypersonic flow was also demonstrated during these tests.

Stewart, David A.↗

NASA NTRS1987

Perovskite oxides: Oxygen electrocatalysis and bulk structure

Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.

Carbonio, R. E.↗

NASA NTRS1988

Perovskite-type oxides - Oxygen electrocatalysis and bulk structure

Carbonio, R. E.↗

NASA NTRS2018

Upgrades to the International Space Station Water Processor Assembly

The International Space Station Water Processor Assembly provides contaminant control and deionization to the Water Recovery System. The Water Processor Assembly presently utilizes sorbent-based Multifiltration Beds and a downstream Catalytic Reactor for these operations. Upgrades and process improvements are desired to improve performance, increase reliability, and decrease consumable resupply. To this end, reverse osmosis membrane separation technologies were evaluated to reduce influent contaminant loads, candidate additives to inhibit wastewater biofilm formation were studied, and life stability testing was completed for a recently developed high-activity catalyst. Evaluation of an adsorption media integration concept was also completed. The performance and applicability of these new technologies within the Water Processor Assembly, as well as their suitability for exploration missions, are discussed herein.

Kayatin, Matthew J.↗

NASA NTRS2007

High-Temperature Desulfurization of Heavy Fuel-Derived Reformate Gas Streams for SOFC Applications

Desulfurization of the hot reformate gas produced by catalytic partial oxidation or autothermal reforming of heavy fuels, such as JP-8 and jet fuels, is required prior to using the gas in a solid oxide fuel cell (SOFC). Development of suitable sorbent materials involves the identification of sorbents with favorable sulfidation equilibria, good kinetics, and high structural stability and regenerability at the SOFC operating temperatures (650 to 800 C). Over the last two decades, a major barrier to the development of regenerable desulfurization sorbents has been the gradual loss of sorbent performance in cyclic sulfidation and regeneration at such high temperatures. Mixed oxide compositions based on ceria were examined in this work as regenerable sorbents in simulated reformate gas mixtures and temperatures greater than 650 C. Regeneration was carried out with dilute oxygen streams. We have shown that under oxidative regeneration conditions, high regeneration space velocities (greater than 80,000 h(sup -1)) can be used to suppress sulfate formation and shorten the total time required for sorbent regeneration. A major finding of this work is that the surface of ceria and lanthanan sorbents can be sulfided and regenerated completely, independent of the underlying bulk sorbent. This is due to reversible adsorption of H2S on the surface of these sorbents even at temperatures as high as 800 C. La-rich cerium oxide formulations are excellent for application to regenerative H2S removal from reformate gas streams at 650 to 800 C. These results create new opportunities for compact sorber/regenerator reactor designs to meet the requirements of solid oxide fuel cell systems at any scale.

Flytzani-Stephanopoulos, Maria↗

NASA NTRSDate not supplied

Pterodactyl: Aerodynamic and Aerothermal Modeling for a Symmetric Deployable Earth Entry Vehicle with Flaps

NASA’s Pterodactyl project has investigated a deployable atmospheric entry vehicle integrated with a flap control system that provides precision targeting during reentry. The control system consists of eight flaps mounted at the edge of a heatshield that can deflect in and out of the flow. An aerodynamic and aerothermodynamic analysis process was developed for preliminary vehicle design and aerodynamic database generation using engineering and CFD tools with varying levels of fidelity. The objective of this analysis was to: 1) understand the inherent aerodynamics, 2) provide an aerodynamics database for stability and control analysis, and 3) provide qualitative and quantitative aeroheating analysis for Thermal Protection System modeling of the flaps. A high fidelity Euler code, Cart3D, was used to resolve complex flow features such as secondary shocks and shock impingement. A wide range of supersonic (Mach 2) and hypersonic Mach numbers (up to Mach 40) were tested with an Earth atmosphere model. A process was developed to utilize the adaptive volume mesh generator utility of the perfect gas model of Cart3D to create meshes with high cell efficiency and numerical stability prior to running a 2nd order accurate solution with a real gas model. High-fidelity aerothermal CFD simulations were performed using US3D to further improve the aerothermal analysis on hypersonic flow around a complex entry vehicle shape including viscosity, chemical reactions of air species, vibrational energy, and catalytic surface reactions. In this process, it was found that the flap control system provided multi-axis control that can be utilized for entry precision targeting. Additionally, the Pterodactyl vehicle can achieve up to a trim L/D of 0.2. Finally, the increased fidelity of the aerothermal heating environments revealed that the shear stress contributes to increasing the heating on the flaps.

Deployable Entry Vehicle↗

NASA NTRSDate not supplied

Pterodactyl: Aerodynamic and Aerothermal Modeling for a Symmetric Deployable Earth Entry Vehicle with Flaps

Deployable Entry Vehicle↗

NASA NTRS1994

The effect of incomplete fuel-air mixing on the lean blowout limit, lean stability limit and NO(x) emissions in lean premixed gas turbine combustors

Gas turbine engines for both land-based and aircraft propulsion applications are facing regulations on NOx emissions which cannot be met with current combustor technology. A number of alternative combustor strategies are being investigated which have the potential capability of achieving ultra-low NOx emissions, including lean premixed combustors, direct injection combustors, rich burn-quick quench-lean burn combustors and catalytic combustors. The research reported in this paper addresses the effect of incomplete fuel-air mixing on the lean limit performance and the NOx emissions characteristics of lean premixed combustors.

Shih, W.-P.↗

NASA NTRS1994

Combined LAURA-UPS solution procedure for chemically-reacting flows

A new procedure seeks to combine the thin-layer Navier-Stokes solver LAURA with the parabolized Navier-Stokes solver UPS for the aerothermodynamic solution of chemically-reacting air flowfields. The interface protocol is presented and the method is applied to two slender, blunted shapes. Both axisymmetric and three dimensional solutions are included with surface pressure and heat transfer comparisons between the present method and previously published results. The case of Mach 25 flow over an axisymmetric six degree sphere-cone with a noncatalytic wall is considered to 100 nose radii. A stability bound on the marching step size was observed with this case and is attributed to chemistry effects resulting from the noncatalytic wall boundary condition. A second case with Mach 28 flow over a sphere-cone-cylinder-flare configuration is computed at both two and five degree angles of attack with a fully-catalytic wall. Surface pressures are seen to be within five percent with the present method compared to the baseline LAURA solution and heat transfers are within 10 percent. The effect of grid resolution is investigated and the nonequilibrium results are compared with a perfect gas solution, showing that while the surface pressure is relatively unchanged by the inclusion of reacting chemistry the nonequilibrium heating is 25 percent higher. The procedure demonstrates significant, order of magnitude reductions in solution time and required memory for the three dimensional case over an all thin-layer Navier-Stokes solution.

Wood, William A.↗

NASA NTRSDate not supplied

Hydrogen Peroxide-Water-Ethanol-Monopropellant Blend for CubeSat Propulsion

Monopropellant propulsion that provides high performance and low hazards compared to state-of-art hydrazine are being investigated under NASA, DOD and commercially sponsored green propellant research and development programs. This NASAeffort looks at phosphate stabilized 50% hydrogen peroxide/water –ethanol blends to evaluate their stability and combustion behavior in submillimeter diameter microtube combustion apparatus for cubesat propulsion applications. Exploratory 7-day stabilitytests find no pressure rise in a sealed test tube environment at room temperature indicating at least short term stability of the mixture. Temperature rise during combustion testing in resistively heated nickel microtube apparatus shows that micro-combustion is achieved in the tube. Propellant density is approximately 1.2 g/cm3compared to 1.0 g/cm3for hydrazine. Theoretical specific impulse of the stoichiometric blend is 219 s at a chamber pressure of 20 psia and an area ratio of 30:1. Density-specific impulseof this blendis263 swhile hydrazine is only about 215-220 sin small reaction control system thrusters. This provides about 20-22% more density-specific impulse for the cubesat compared to hydrazine. The theoreticalcombustion temperature is2168°F, whichis thermally compatible with stainless steel materials of constructionand the nickel catalystused in the tests. Combustion test results are given for stoichiometric, as well as fuel-leanand fuel-richpropellant formulations. Thesetests focus on thermally and catalytically supported combustionin the microtube, whichrequires a microtube preheat temperature of about 900°F and sufficient residence time to achieve combustion that is stable and anchored in the tubewithout blowing through the tube unreacted. Thrust class is expected to be in the 10 mN range based on flow rate and estimated specific impulse.Power requirements are generally below 25 Wto heat the tube. Steady state combustion testing is typically conducted for 3 minutes and shows littledegradation of the hardware over multiple test cyclesindicating thatthere is little catalyst degradation over time and littlecatalyst deactivation due tothe phosphate stabilizer inthe hydrogen peroxide.

Monopropellant↗

NASA NTRS1997

New Approaches to Waterproofing of Space Shuttle Insulating Materials

Future reusable space vehicles will be in service much more frequently than current space shuttles. Therefore, rapid reconditioning of spacecraft will be required. Currently, the waterproofing of space shuttles after each re-entry takes 72 hours and requires substantial labor. In addition, the currently used waterproofing reagent, DiMethylEthoxySilane (DMES), is considered toxic, and ethanol fumes are released during its hydrolytic activation. Consequently, a long time period, which is not acceptable for future operations, is needed to ensure that 0 the excess volatile compounds are removed before further maintenance of the space vehicle can be performed. The objective of this project was to assist NASA Ames in finding improved waterproofing systems by identifying suitable waterproofing agents that can be applied by vapor phase deposition and will be less toxic, bond more rapidly to the insulation material surface, and potentially have higher thermal stability than the DMES system. Several approaches to achieve faster waterproofing with less toxicity were assessed using the following alternatives: Reactive volatile compounds that are rapidly deposited by chemical bonding at the surface and leave no toxic volatiles. Reactive reagents that are the least toxic. Nonvolatile reagents that are very reactive and bond strongly to the insulating material surface. Three specific types of potential reagents were chosen for evaluation in this project: 1. Volatile reagents with Si-Cl functional groups for vapor deposition 2. Volatile reagents with Si-H functional groups for vapor deposition 3. Nonvolatile oligomeric or polymeric reactive siloxanes that are assumed to have higher thermal stability and/or strong bonding to the insulating material. The chemistry involved in the project was targeted at the generation of intermediates having reactive Si-OH bonds for the formation of either volatile species or polymeric species that bond rapidly to the surface and also cure rapidly. We focused on two chemical reactions@-hydrolysis of Si-Cl bonds and catalytic dehydrocoupling of Si-H bonds.

Blum, Yigal D.↗

NASA NTRS2014

Aura OMI Observations of Global SO2 and NO2 Pollution from 2005 to 2013

The Ozone Monitoring Instrument (OMI), a NASA partnership with the Netherlands and Finland, flies on the NASA Aura satellite and uses reflected sunlight to measure the two critical atmospheric trace gases: nitrogen dioxide (NO2) and sulfur dioxide (SO2) characterizing daily air quality. Both gases and the secondary pollutants they produce (particulate matter, PM2.5, and tropospheric ozone) are USEPA designated criteria pollutants, posing serious threats to human health and the environment (e.g., acid rain, plant damage and reduced visibility). Our group at NASA GSFC has developed and maintained OMI standard SO2 and NO2 data products. We have recently released an updated version of the standard NO2 L2 and L3 products (SP v2.1) and continue improving the algorithm. We are currently in the process of releasing next generation pollution SO2 product, based on an innovative Principal Component Analysis (PCA) algorithm, which greatly reduces the noise and biases. These new standard products provide valuable datasets for studying anthropogenic pollution on local to global scales. Here we highlight some of the OMI observed changes in air quality over several regions. Over the US average NO2 and SO2 pollution levels had decreased dramatically as a result of both technological improvements (e.g., catalytic converters on cars) and stricter regulations of emissions. We see continued decline in pollution over Europe. Over China OMI observed an increase of about 60 percent in NO2 pollution between 2005 and 2013, despite a temporal reversal of the growing trend due to both 2008 Olympic Games and the economic recession in 2009. Chinese SO2 pollution seems to have stabilized since peaking in 2007, probably due to government efforts to curb SO2 emissions from the power sector. We have also observed large increases in both SO2 and NO2 pollution particularly in Eastern India where a number of large new coal power plants had been built in recent years. We expect that further improvements in the OMI NO2 and SO2 products will allow more robust quantification of long-term trends in global air quality.

SO2↗

NASA NTRSDate not supplied

Hydrogen Peroxide-Water-Ethanol Monopropellant Blend for CubeSat Propulsion

Monopropellant propulsion that provides high performance and low hazards compared to state-of-art hydrazine are being investigated under NASA, DOD and commercially sponsored green propellant research and development programs. This NASA effort looks at phosphate stabilized 50% hydrogen peroxide/water –ethanol blends to evaluate their stability and combustion behavior in submillimeter diameter microtube combustion apparatus for cubesat propulsion applications. Exploratory 7-day stability tests find no pressure rise in a sealed test tube environment at room temperature indicating at least short term stability of the mixture. Temperature rise during combustion testing in resistively heated nickel microtube apparatus shows that micro-combustion is achieved in the tube. Propellant density is approximately 1.2 g/cu.cm compared to 1.0 g/cu.cm for hydrazine. Theoretical specific impulse of the stoichiometric blend is 219 s at a chamber pressure of 20 psia and an area ratio of 30:1. Density-specific impulse of this blend is 263 s while hydrazine is only about 215-220 s in small reaction control system thrusters. This provides about 20-22% more density-specific impulse for the cube sat compared to hydrazine. The the oretical combustion temperature is 2168°F, which is thermally compatible with stainless steel materials of construction and the nickel catalyst used in the tests. Combustion test results are given for stoichiometric, as well as fuel-lean and fuel-rich propellant formulations. These tests focus on thermally and catalytically supported combustion in the microtube, which requires a microtube preheat temperature of about 900°F and sufficient residence time to achieve combustion that is stable and anchored in the tube without blowing through the tube unreacted. Thrust class is expected to be in the 10 m N range based on flow rate and estimated specific impulse. Power requirements are generally below 25 W to heat the tube. Steady state combustion testing is typically conducted for 3 minutes and shows little degradation of the hardware over multiple test cycles indicating that there is little catalyst degradation over time and little catalyst deactivation due to the phosphate stabilizer in the hydrogen peroxide.

Monopropellant↗

NASA NTRS1997

Application of Shear Plate Interferometry to Jet Diffusion Flame Temperature Measurements

The recent ban on the production of bromotrifluoromethane (CF3Br) because of its high stratospheric ozone depletion potential has led to interest in finding alternative agents for fire extinguishing applications. Some of the promising alternatives are fluorinated hydrocarbons. A clear understanding of the effects of CF3Br and alternative chemical suppressants on diffusion flames is therefore necessary in the selection of alternative suppressants for use in normal and microgravity. The flame inhibition effects of halogen compounds have been studied extensively in premixed systems. The effect of addition of halocarbons (carbon-halogen compounds) to diffusion flames has been studied experimentally in coflow configurations and in counterflow gaseous and liquid-pool flames. Halogenated compounds are believed to inhibit combustion by scavenging hydrogen radicals to form the relatively unreactive compound HF, or through a catalytic recombination cycle involving HBr to form H2. Comparisons between halogens show that bromine inhibition is significantly more effective than chlorine or fluorine. Although fluorinated compounds are only slightly more effective inhibitors on a mass basis than nitrogen, they are more effective on a volume basis and are easily stored in liquid form. The objectives of this study are (a) to determine the stability limits of laminar jet diffusion flames with respect to inhibitor concentration in both normal and microgravity, and (b) to investigate the structure of halocarbon-inhibited flames. In the initial phase of this project, visual diagnostics were used to observe the structure and behavior of normal and microgravity flames. The initial observations showed significant changes in the structure of the flames with the addition of halocarbons to the surrounding environment, as discussed below. Furthermore, the study established that the flames are more stable relative to the addition of halocarbons in microgravity than in normal gravity. Visual diagnostics of flames are, however, necessarily limited to detection of radiative emission in the visible range, and offer only qualitative information about the nature of the processes in the flame. In particular, the study sought to understand the structure of the inhibitor-perturbed flames with regard to temperature and species concentration in the outer region of the flame. Whereas thermocouple measurements can be used in ground based studies, their implementation in drop-tower rigs is limited. A possible approach to determine the temperature field around the flame is to use interferometric techniques. The implementation and testing of a shear-plate interferometry technique is described below.

VanDerWege, Brad A.↗